US8614875B2 - Anchor group for monolayers of organic compounds on metal and component produced therewith by means of organic electronics - Google Patents

Anchor group for monolayers of organic compounds on metal and component produced therewith by means of organic electronics Download PDF

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US8614875B2
US8614875B2 US12/998,157 US99815709A US8614875B2 US 8614875 B2 US8614875 B2 US 8614875B2 US 99815709 A US99815709 A US 99815709A US 8614875 B2 US8614875 B2 US 8614875B2
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capacitor
copper
group
anchor group
phosphonic acid
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US20110170227A1 (en
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Günter Schmid
Dan Taroata
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Siemens AG
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Definitions

  • Organic dielectric or conductive compounds on metal electrodes are used, for example, in the production of organic-based electronic components.
  • ultrathin layers especially monolayers
  • ultrathin layers with precisely adjusted functionality in electronic components, especially also in organic electronic components.
  • head or anchor groups which automatically results in an alignment of the linker groups, i.e. of the groups connecting the two ends.
  • the attachment to the substrate takes place spontaneously provided that the substrate has been prepared appropriately.
  • the specific functionality is determined by the linkers and head groups.
  • the anchor determines the self-organization.
  • DE 10 2004 005 082 discloses an aromatic head group which has ⁇ - ⁇ interaction and whose introduction is chemically complex, which binds a self-assembled dielectric layer to an electrode.
  • the attachment to the counterelectrode used as what is called the anchor group of the organic dielectric compound, which is usable as a monolayer in a capacitor, is a silane compound which can be attached to the electrode via an oxide layer formed from a non-copper oxide.
  • the electrode surface i.e., for example, the copper surface
  • the electrode surface preferably has to be functionalized with aluminum or titanium for application of the self-assembled monolayer, the functionalization then providing an oxidic surface for attachment.
  • a functionalization step for the electrode surface is very costly, since non-copper metals first have to be applied and structured.
  • the electrode surfaces, if they are processed by conventional methods on conventional blanks or circuit boards or prepregs generally have a surface roughness in the region of approx. 4 ⁇ m. This roughness limits the mechanical stability of a surface coated with a monolayer, since the gaps at the particle boundaries are not necessarily fully covered, or high field strengths arise at substrate tips.
  • the height of the monolayer generally approx. 2 to 5 nm, and not more than 20 nm, does not planarize the roughness due to the conforming deposition.
  • an organic compound for a self-assembled monolayer on a copper layer or copper-containing layer comprising at least one anchor group for a first electrode layer, a linker group and a head group for attachment to the next layers, wherein the anchor group contains at least one phosphonic acid and/or a phosphonic acid derivative.
  • the head group may be of a specific type, or else be dispensed with.
  • the inventors propose a component which is based on organic electronics and is integrated into a circuit board, a prepreg or a blank, wherein the blank, circuit board or prepreg serves as a substrate on which an organic compound for a self-assembled monolayer according to the subject matter of the proposals (see above) is formed.
  • organic compound for a self-assembled monolayer refers above to compounds which, due to a particular anchor group, are aligned in the layer such that a majority of the molecules are present with parallel and/or identical alignment in the layer.
  • DE 10 2004 005082 describes corresponding organic compounds which can form monolayers in the dielectric layer of a component based on organic electronics.
  • the organic compounds usable differ from these at least by a different head and/or anchor group.
  • many commercially available materials can be employed and used to produce impervious monolayers.
  • a component based on organic electronics is formed directly on a blank, for example a copper blank produced by customary production methods, without having been functionalized by a further metal or smoothed by specific processes.
  • the metal layer to which the anchor group is applied is accordingly a copper layer or copper-containing layer, the proportion of copper in the layer being preferably more than 10%, especially preferably more than 40% and most preferably more than 70%, measured in mole percent.
  • the preparation includes only cleaning steps and not the application of additional materials, as is customary according to the art.
  • a useful component based on organic electronics is especially a capacitor.
  • organic field-effect transistors the gate dielectric for organic field-effect transistors being suitable for direct integration into the circuit board, or organic light-emitting diodes (OLEDs), the electrodes for the OLEDs being deposited on the thin insulation, especially since the copper layer for top-emitting OLEDs is hermetic.
  • OLED also includes light-emitting electrochemical cells (LEECs).
  • the layer sequence can also be used for solar cells, and so possible components based on organic electronics are, as well as capacitors, at least also organic field-effect transistors, OLEDs and organic solar cells.
  • the proposals are suitable for all kinds of organic insulating intermediate layers.
  • the layer can also be applied only for a certain time, i.e. temporarily. Applied in a temporary or permanent manner to copper or copper alloys, the layer is also suitable as a printable “photoresist substitute”, or for production of regions of different hydrophobicity.
  • FIG. 1 shows such a structure using the example of a capacitor.
  • FIG. 2 visualizes the roughness of a pickled circuit board substrate.
  • FIGS. 3 and 4 show the electrical characteristics (value approx. 10 ⁇ and phase angle of the impedance approx. 0°) assuming all capacitors are short-circuited.
  • FIG. 5 shows a spin curve, with the effective mean layer thickness of the polymer layer shown as a function of the spin speed.
  • FIG. 6 shows the dependence of the capacitance on the frequency.
  • FIG. 7 shows the dependence of the phase of the impedance on the frequency.
  • FIG. 8 shows the dependence of the phase of the loss factor on the frequency.
  • FIG. 9 shows the dependence of integration density 49 pF/mm 2 on the direct current voltage applied for a capacitor having a nominal integration density of 49 pF/mm 2 .
  • FIGS. 10 to 13 show the dependence of the capacitance on the electrode area at 0 V to 3 V at 50 pF/mm 2 .
  • FIG. 14 shows the leakage current measurement for a capacitor with an integration density of 50 pF/mm 2 , for round electrodes.
  • FIG. 15 shows the leakage current measurement for a capacitor with an integration density of 50 pF/mm 2 , for angular electrodes.
  • FIG. 16 shows a roughness within the range from 0.20 nm to 0.33 nm.
  • FIG. 17 shows the homogeneity of vapor-deposited layers.
  • FIG. 18 shows the measurement to determine the relative dielectric constants.
  • FIG. 19 shows the dependence of the capacitance on the frequency of capacitors with an integration density of 150 pF/mm 2
  • FIG. 20 shows the dependence of the phase on the frequency of capacitors with an integration density of 150 pF/mm 2
  • FIG. 21 shows the dependence of the loss factor on the frequency of capacitors with an integration density of 150 pF/mm 2
  • FIG. 22 shows the dependence of leakage current characteristics as a function of voltage for different capacitors
  • FIG. 23 shows the resistance of the capacitor to DC current at different integration densities.
  • FIG. 24 shows the dependence of the contact angle measured after the SAM coating of the circuit board on the insertion time of the sample in the solution.
  • FIG. 1 shows such a structure using the example of a capacitor.
  • the base material used for the capacitor is a copper blank pickled by customary methods with an applied layer of approx. 5-30 ⁇ m of copper plate and a roughness in the ⁇ m range.
  • the pickling can be effected as usual by degreasing with organic solvents and then etching the surface with peroxodisulfates and sulfuric acid.
  • FIG. 2 visualizes the roughness of a pickled circuit board substrate.
  • the copper surface can be additionally cleaned, as usual in electroplating technology, by cathodic means.
  • the substrate is connected as the cathode in dilute sodium carbonate solution and cleaned by the hydrogen which forms at a current flow of 10-100 mA/cm 2 .
  • the contact angle with respect to water is less than 5°.
  • the copper surface becomes very hydrophilic.
  • a monolayer of an organic phosphonic acid is deposited immediately thereafter.
  • the phosphonic acid anchor group has been found to be highly suitable especially for copper, whereas DE10 2004 005082 B4 worked preferably with silanes (working example), and the copper surface preferably has to be functionalized with aluminum or titanium for deposition. Such a functionalization step for the copper surface is dispensed with completely in the component presented.
  • the molecule chain may also take the form of a polyether chain (—O—CH 2 —CH 2 —O—) m where m is from 1 to 20, preferably from 2 to 10.
  • the contact angle with respect to water increases after deposition of an octadecylphosphonic acid to >130° for alkylphosphonic acids, and is thus an indication of the quality of the deposition.
  • the alkyl chains may also be fully or partly fluorinated.
  • the deposition can also be effected via the phosphonic esters or salts thereof, or other derivatives such as amines etc.
  • the salts can be obtained directly in solution by adding smaller or equivalent amounts of alkali (NaOH, KOH, ammonia or ammonium hydroxides).
  • the head group used in the case of a support polymer may be singly branched or unbranched alkyl groups, or alkenyl groups suitable for further reactions (i.e. crosslinking).
  • the head group may be a fluorine, nitrile, amino, ester, aldehyde, epoxy or acid function.
  • the head group could comprise —CF 3 , —CHF 2 , —CH 2 F.
  • a support polymer i.e. a thin polymer layer
  • a support polymer is applied to the monolayer for stabilization and/or for the local planarization of the capacitor or component.
  • an effective polymer layer thickness of approx. 550-600 nm is obtained for an integration density of 50 pF/mm 2 at a dielectric constant of 3.17, whereas an effective layer thickness of 180-200 nm is obtained for an integration density of 150 pF/mm 2 .
  • More polymer is applied in the depressions, while a thinner polymer film is present at the peaks.
  • the component thickness of 14 ⁇ m can be lowered by a factor of 70 while simultaneously increasing the capacitance by a factor of 15.
  • the leakage current characteristics of the capacitor disclosed here are determined almost exclusively by the self-assembled monolayer. It was therefore also measured (see FIG. 24 ) that the resistances have profiles independent of the stabilization polymer thickness because the essential contribution to the ohmic overall resistance of the capacitor to direct current is made by the self-assembled monolayer. It is therefore possible to planarize using any desired polymers, provided that they are compatible with the circuit board processes.
  • polyhydroxystyrene crosslinked by melamine-co-formaldehyde was used.
  • a good planarizing action was achieved when the polyhydroxystyrene had a molar mass in the range from 500 to 100 000, especially from 3500 to 50 000, especially preferably of 8000.
  • the crosslinking was preferably performed within the temperature range between 180° C.-230° C. After the crosslinking, the polymer layer for mechanical stabilization is no longer attacked by solvents.
  • polyesters polyamides, polyimides, polybenzoxazoles, polyvinylidene difluoride (teflon-like materials in general), polyvinyl compounds (carbazoles, alcohols and esters thereof).
  • Copolymers or block copolymers such as ABS are likewise suitable.
  • the molar mass of the polymers may be in the range from 1000 to 1 000 000.
  • the locally planarized polymer layers may be applied as follows:
  • the outer electrodes used for the capacitor may be any metal or alloy thereof, or conductive metallic printing pastes.
  • organic conductors such as PEDOT (polystyrenesulfonic acid-doped polydiethoxythiophene) or PANI (camphorsulfonic acid-doped polyaniline).
  • PEDOT polystyrenesulfonic acid-doped polydiethoxythiophene
  • PANI camphorsulfonic acid-doped polyaniline
  • metals used in the circuit board industry copper, aluminum, nickel, gold and silver or alloys thereof.
  • Metal counterelectrodes applied over the full area can be structured thereafter by etching and mechanical ablation processes (laser) known to those skilled in the art. When several capacitors are provided with a common counterelectrode, the counterelectrode can also be deposited from the gas phase by shadowmasks (see working examples).
  • the counterelectrodes can also be applied by electroless metallization, after local or full-area seeding. In principle, it is possible to use all processes in the circuit board industry, since the dielectric after crosslinking is compatible with the customary media in the circuit board industry.
  • the head group normally stabilizes the monolayer itself.
  • the head group brings about the attachment of the SAMs to the opposite layer.
  • Attachment is understood here to mean any form of the bond, especially a chemical bond, which can range from a covalent double bond through ionic bonds up to simple van der Waals bonds.
  • the head group does not come into contact with the electrode in a capacitor with a stabilizing polymer outer layer, as envisaged in an advantageous embodiment. Only the polymer layer comes into contact with the outer electrode.
  • the polymer layer can be functionalized by the known processes, for example by metal application by vapor deposition or sputtering, printing with metal pastes, etc. It has been found experimentally that it is then also possible to dispense with an inconvenient head group.
  • the interaction of the individual chains is in principle sufficient for the stabilization of the self-assembled monolayer, but a head group can improve the electrical properties even in the case of use of a polymer outer layer to stabilize the monolayer.
  • a gate dielectric for organic field-effect transistors for direct integration into the circuit board.
  • a substrate for top-emitting OLED (the copper layer is hermetic). On the thin insulation, it is then possible to deposit the electrodes for the OLED.
  • the layer sequence is also suitable for solar cells.
  • an FR4 blank laminated with 30 ⁇ m of copper is cut to a size of 50 ⁇ 50 m 2 . This is first freed of grease with acetone and isopropanol.
  • a commercial photoresist (TMSR8900) is spun on at 6000 rpm for 20 s and dried on a hotplate at 110° C. for 60 s. The photoresist is exposed for 7 s with UV light of a wavelength of 365 nm, and developed in aqueous alkaline developer for 60 s.
  • the photostructuring is followed by pickling in a 5% ammonium peroxodisulfate solution at 40° C. for 3 min. After rinsing with water and isopropanol, the blank is placed into a solution of octadecylphosphonic acid (0.2-0.25 g) in isopropanol (100 ml). After 12 hours, the blank is rinsed with isopropanol and dried in a nitrogen stream at 100° C. for 1 min.
  • the contact angle with respect to water is 1° to 4°.
  • the contact angle is 135°, which suggests excellent coverage of the copper layer.
  • 100 nm of aluminum is applied by vapor deposition through a shadowmask as the counterelectrode.
  • a processed capacitance specimen was thus produced on an FR4 circuit board.
  • the electrical characteristics (value approx. 10 ⁇ and phase angle of the impedance approx. 0°) in FIGS. 3 and 4 show that all capacitors are short-circuited.
  • An ideal capacitor would have a volume resistance of infinity. 10 ohms is a short circuit, i.e. the capacitor does not work. It is found that, for standard circuit boards with a roughness in the ⁇ m range without Ti or Al pretreatment or without the presence of an aromatic head group on the primer, the process from DE 10 2004 005082 is not suitable for formation of capacitors in high yield.
  • high-capacitance capacitors can be formed directly on copper with a primer even without a head group with ⁇ - ⁇ interaction, the introduction of which is chemically complex.
  • the anchor group i.e. the phosphonic acid group, resides directly on the copper surface.
  • a copper-laminated FR4 circuit board or a prepreg is coated with the primer octadecylphosphonic acid or hexadecylphosphonic acid.
  • a solution of 0.8 g of polyvinyl-phenol (molar mass 8000) containing 0.2 g of polymelamine-co-formaldehyde crosslinker is dissolved in 5.67 g of propylene glycol monomethyl ether acetate and spun on at 2500 rpm for 40 s, and predried on a hotplate at 100° C. for 60 s. In a vacuum oven, the novolac-like polymer is cured with the formaldehyde crosslinker at 180° C. to 230° C.
  • aluminum electrodes are applied by vapor deposition (base pressure 1*10 ⁇ 6 mbar). Other integration densities can be obtained by adjusting the spin speed.
  • FIG. 5 shows a spin curve, with the effective mean layer thickness of the polymer layer shown as a function of the spin speed.
  • FIGS. 6 to 9 show the dependence of the capacitance ( 6 ), of the phase of the impedance ( 7 ) and of the loss factor ( 8 ) of an actual capacitor with integration density 49 pF/mm 2 ( 9 ) on the frequency and direct current voltage applied.
  • the electrical characteristics are shown in FIGS. 6 to 9 .
  • the dependence of the capacitance measured on the frequency is low, which demonstrates the quality of the capacitor presented.
  • the phase of the impedance of the actual capacitor assumes values between ⁇ 89° and ⁇ 87° in the frequency range shown.
  • the loss factor was in the region of 0.0x and is, as shown in FIG. 8 , likewise virtually independent of the frequency.
  • bias voltages between 0 V and 3 V were set, while the amplitude of the superimposed alternating current, the frequency of which was varied between 1 kHz and 1 MHz, was 0.1 V.
  • FIGS. 10 to 13 show the dependence of the capacitance on the electrode area.
  • the yield of functioning substrates is 100% on a substrate according to example 1.
  • the quality of the capacitors is thus comparable to discrete SMD components (loss factor of 0.035 in commercial ceramic SMD capacitors).
  • FIGS. 10 to 13 show the dependence of the capacitance on the electrode area at 0 V to 3 V at 50 pF/mm 2 .
  • FIGS. 14 and 15 show the leakage current measurement for a capacitor with an integration density of 50 pF/mm 2 and ( 14 ) round or ( 15 ) angular electrodes.
  • FIGS. 14 and 15 show the leakage current measured as a function of the direct current voltage applied in capacitors with different electrode areas.
  • the measurement curves do not show an actual breakthrough, but merely an increased leakage current from 7 V DC (2 nA to 4 nA), but this is small compared to SMD components. Moreover, there is no evident dependence of the currents measured in FIGS. 14 and 15 on the electrode shape.
  • the dielectric constant of the crosslinked polymer was determined as follows. Owing to the excessive roughness of the FR4 substrate (see FIG. 2 ), an exact determination of the dielectric thickness is impossible. For this reason, capacitors were produced on a substrate with minimum roughness. For this purpose, glass substrates were used as carriers. With the aid of a profilometer, the profile of such a substrate was first examined. FIG. 16 shows the roughness measurement on a glass sample.
  • the roughness is within the range from 0.20 nm to 0.33 nm.
  • both electrodes were applied to the substrate by a vapor deposition process.
  • the homogeneity of the vapor-deposited layers is shown in FIG. 17 .
  • a 100 nm-thick copper layer was applied by vapor deposition.
  • the corners of the glass sample were masked with Kapton tape as a shadowmask.
  • the Kapton tape was removed and the layer thickness was measured with the aid of a profilometer.
  • the polymer layer was applied by spin-coating (20% by weight polymer solution, spin speed 2500 rpm). Before this processing step, the sample was provided again with Kapton tape at one corner. This created a defined level at which the thickness of the dielectric can be determined. The subsequent layer thickness measurement gave an effective mean thickness of 573 nm. With the aid of another vapor deposition step, the upper electrode of the capacitors was produced.
  • FIG. 18 shows the measurement to determine the relative dielectric constants.
  • a copper-laminated FR4 circuit board or a prepreg was coated with the primer octadecylphosphonic acid or hexadecylphosphonic acid.
  • a photochemically crosslinking epoxy resin is used. The photocrosslinking is performed, for example, through a shadowmask. After the uncrosslinked regions have been rinsed off, there remain defined dielectric regions. Contact sites are exposed.
  • the counterelectrode may be a copper electrode, which is applied, for example, by sputtering.
  • FIGS. 19 to 22 The electrical characteristics of the capacitors with an integration density of 150 pF/mm 2 are shown in FIGS. 19 to 22 .
  • FIGS. 19 to 22 show the dependence of the capacitance ( 19 ), of the phase ( 20 ) and of the loss factor ( 21 ) on the frequency and leakage current characteristics ( 22 ) of the capacitors with an integration density of 150 pF/mm 2 as a function of the capacitance value (or electrode area).
  • FIG. 19 shows the essentially frequency-independent behavior of capacitance of a capacitor of area 1 mm 2 .
  • the loss factor was in the range of 0.05-0.3 and is, as shown in FIG. 21 , likewise virtually independent of the frequency.
  • FIG. 22 shows the leakage current measured for capacitors with different electrode areas. The measurement results are essentially independent of the capacitance value and hence of the electrode area. In addition, the currents measured are comparable to those in example 2, FIGS. 6 and 7 .
  • FIG. 19 shows the essentially frequency-independent behavior of capacitance of a capacitor of area 1 mm 2 .
  • the loss factor was in the range of 0.05-0.3 and is, as shown in FIG. 21 , likewise virtually independent of the frequency.
  • FIG. 22 shows the leakage current measured for capacitors with different electrode areas. The measurement results are essentially independent of the capacitance value and hence of the electrode area. In addition, the currents measured are comparable to those in example 2, FIGS. 6 and 7 .
  • FIG. 19 shows the
  • FIG. 23 shows the resistance of the capacitor to DC current at different integration densities.
  • FIG. 23 shows that the essential contribution to the ohmic overall resistance of the capacitor to direct current is made by the self-assembled monolayer.
  • the quality of the SAM layer deposited is therefore paramount firstly for the good insulation properties and secondly for a good yield of the actual capacitors.
  • FIG. 24 shows that the process has low dynamics. After an insertion time of 10 seconds, the contact angle is only 1.1° less than after 10 minutes, and 1.9° less than after one hour. The angle then remains, after repeated measurements, at a mean of 135° ⁇ 0.8°, even after 72 hours of insertion time of the samples in the SAM solution.
  • FIG. 24 shows the dependence of the contact angle measured after the SAM coating of the circuit board on the insertion time of the sample in the solution.
  • the polymer layer is in the form of ABS (acrylonitrile-butadiene-styrene). This is structurally seeded with palladium by standard methods and the outer electrodes of copper or nickel are deposited electrolessly.
  • ABS acrylonitrile-butadiene-styrene
  • capacitors which can be produced in a parallel process on a prepreg or other common circuit board substrates are described for the first time. Thereafter, the prefabricated capacitor layer can be integrated into the circuit board, which results in a space/cost saving for the surface of the circuit board.
  • the topography of the capacitor is extremely small in relation to the roughness of the base substrate.
  • the related art assumes that it is not possible to deposit self-assembled monolayers on copper. It is shown here that self-assembled monolayers (SAMs) with phosphonic acid anchors can be deposited very efficiently and rapidly on copper after the copper surface has been cleaned appropriately. This layer constitutes the actual insulation layer of the capacitor. For mechanical stabilization, a thin polymer layer is applied to the SAM.
  • the outer contact may take various forms.

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DE102009016659A1 (de) 2008-09-23 2010-06-24 Siemens Aktiengesellschaft Ankergruppe für Monolagen organischer Verbindungen auf Metall und damit hergestelltes Bauelement auf Basis organischer Elektronik
DE102010063718A1 (de) * 2010-12-21 2012-06-21 Siemens Aktiengesellschaft Dielektrische Schicht für ein elektrisches Bauelement, elektrisches Bauelement mit dielektrischer Schicht und Verfahren zum Herstellen eines elektrischen Bauelements mit dielektrischer Schicht
JP6190104B2 (ja) * 2012-11-01 2017-08-30 Ｄｏｗａメタルテック株式会社 ニッケルめっき材およびその製造方法
KR101525152B1 (ko) * 2012-12-12 2015-06-04 영창케미칼 주식회사 커패시터 쓰러짐 방지용 코팅 조성물
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DE102013202252A1 (de) * 2013-02-12 2014-08-28 Siemens Aktiengesellschaft Dünnschichtkondensatoren mit hoher Integrationsdichte
CN105355785A (zh) * 2015-09-23 2016-02-24 重庆大学 一种n型有机场效应晶体管的制备方法
DE102015220490A1 (de) * 2015-10-21 2017-04-27 Robert Bosch Gmbh Superkondensator, dessen Kollektoren mit einem elektrisch leitfähigen Oligomer oder Polymer beschichtet sind, und Verfahren zu dessen Herstellung
US11069526B2 (en) * 2018-06-27 2021-07-20 Taiwan Semiconductor Manufacturing Co., Ltd. Using a self-assembly layer to facilitate selective formation of an etching stop layer
CN110783727A (zh) * 2018-11-09 2020-02-11 广州方邦电子股份有限公司 一种连接器及制作方法
KR20220060286A (ko) 2020-11-04 2022-05-11 삼성전기주식회사 적층형 커패시터
KR20220074262A (ko) * 2020-11-27 2022-06-03 삼성전기주식회사 적층형 커패시터

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WO2010034597A2 (de) 2010-04-01
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CN102165101B (zh) 2014-06-25
WO2010034597A3 (de) 2010-06-10
EP2326746A2 (de) 2011-06-01
DE102009016659A1 (de) 2010-06-24
US8842414B2 (en) 2014-09-23
US20110170227A1 (en) 2011-07-14
JP2012503097A (ja) 2012-02-02
EP2706585A2 (de) 2014-03-12
CN102165101A (zh) 2011-08-24
US20140060900A1 (en) 2014-03-06

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